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US4582679A - Titanium nitride dispersion strengthened alloys - Google Patents

Titanium nitride dispersion strengthened alloys Download PDF

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Publication number
US4582679A
US4582679A US06/715,378 US71537885A US4582679A US 4582679 A US4582679 A US 4582679A US 71537885 A US71537885 A US 71537885A US 4582679 A US4582679 A US 4582679A
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United States
Prior art keywords
titanium
heating
temperature
alloy powder
powder
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Expired - Lifetime
Application number
US06/715,378
Inventor
Eric G. Wilson
Andrew M. Wilson
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Accentus Medical PLC
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UK Atomic Energy Authority
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Publication date
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Assigned to UNITED KINGDOM ATOMIC ENERGY AUTHORITY reassignment UNITED KINGDOM ATOMIC ENERGY AUTHORITY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: WILSON, ANDREW M., WILSON, ERIC G.
Application granted granted Critical
Publication of US4582679A publication Critical patent/US4582679A/en
Assigned to AEA TECHNOLOGY PLC reassignment AEA TECHNOLOGY PLC TRANSFER BY OPERATION OF LAW Assignors: UNITED KINGDOM ATOMIC ENERGY AUTHORITY
Assigned to ACCENTUS PLC reassignment ACCENTUS PLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AEA TECHNOLOGY PLC
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0068Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14Treatment of metallic powder
    • B22F1/145Chemical treatment, e.g. passivation or decarburisation

Definitions

  • This invention relates to titanium nitride dispersion strengthened alloys and their production.
  • particles of titanium-containing alloy powder which also contains chromium are heated in the presence of ammonia to form a layer of chromium nitride(s) on the particles and then in an inert atmosphere at a higher temperature to dissociate the chromium nitride(s) and convert substantially all titanium present to titanium nitride.
  • the chromium nitride(s) (CrN/CrN 2 ) forming the layer on the particles after treatment with ammonia can provide a high activity source of nitrogen in an envelope around each particle for reaction with the titanium present and that this is an improvement on a previously proposed route which depended upon transport of nitrogen from nitrided (CrN/CrN 2 ) particles to un-nitrided particles in a blended mixture of the two.
  • the invention is considered particularly applicable to titanium containing stainless steel and nickel based alloy powders which are subsequently to be formed into fuel element containers or other nuclear reactor components and have a particle size between 30 and 120 microns.
  • An example of a stainless steel is a 20Cr/25Ni alloy containing up to 2 wt /o Ti.
  • An example of a nickel based alloy is that known as Nimonic PE16.
  • Such components may be formed by conventional powder metallurgy techniques, for example, powder extrusion. In particular they may be formed into tubing.
  • a suitable temperature for the treatment with ammonia is about 700° C. and for the subsequent homogenisation between 1000° C. and 1150° C. By homogenisation is meant the high temperature transport of nitrogen from the chromium nitride layer.
  • the atmosphere during the homogenising stage may be a hydrogen/nitrogen mixture to maintain a suitable nitrogen activity.
  • the duration of treatment is extended beyond completion of the formation of the titanium nitride by changing the atmosphere to hydrogen to remove excess nitrogen which could form embrittling phases in service if allowed to remain in solid solution.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Abstract

To increase the creep strength of a titanium-containing alloy which also contains chromium, the alloy powder is heated in the presence of ammonia at a temperature of the order of 700° C. so as to form a layer of chromium nitride(s) on the particles and is then heated further in an inert atmosphere at a temperature between 1000° C. and 1150° C. to dissociate the chromium nitride(s) thereby effecting nitriding of the titanium to titanium nitride which affords dispersion-strengthening of the alloy.

Description

BACKGROUND OF THE INVENTION
This invention relates to titanium nitride dispersion strengthened alloys and their production.
It is known that the creep strength of certain titanium-containing alloys can be increased by the presence of titanium nitride dispersions and that such dispersions can be introduced by treatment of the alloys in powder form. It is also known that when the alloys also contain chromium and nitriding is attempted by heating in ammonia relatively small penetration of the titanium nitride front normally occurs.
FEATURES AND ASPECTS OF THE INVENTION
According to the present invention particles of titanium-containing alloy powder which also contains chromium are heated in the presence of ammonia to form a layer of chromium nitride(s) on the particles and then in an inert atmosphere at a higher temperature to dissociate the chromium nitride(s) and convert substantially all titanium present to titanium nitride.
It is considered that the chromium nitride(s) (CrN/CrN2) forming the layer on the particles after treatment with ammonia can provide a high activity source of nitrogen in an envelope around each particle for reaction with the titanium present and that this is an improvement on a previously proposed route which depended upon transport of nitrogen from nitrided (CrN/CrN2) particles to un-nitrided particles in a blended mixture of the two.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention is considered particularly applicable to titanium containing stainless steel and nickel based alloy powders which are subsequently to be formed into fuel element containers or other nuclear reactor components and have a particle size between 30 and 120 microns. An example of a stainless steel is a 20Cr/25Ni alloy containing up to 2 wt /o Ti. An example of a nickel based alloy is that known as Nimonic PE16. Such components may be formed by conventional powder metallurgy techniques, for example, powder extrusion. In particular they may be formed into tubing. A suitable temperature for the treatment with ammonia is about 700° C. and for the subsequent homogenisation between 1000° C. and 1150° C. By homogenisation is meant the high temperature transport of nitrogen from the chromium nitride layer. It includes dissociation, diffusion and chemical reaction processes and can be achieved by heating the powder rapidly to the dissociation temperature, for example, by pouring the powder into a hot furnace or by increasing the temperature of the nitriding furnace. The atmosphere during the homogenising stage may be a hydrogen/nitrogen mixture to maintain a suitable nitrogen activity. Preferably the duration of treatment is extended beyond completion of the formation of the titanium nitride by changing the atmosphere to hydrogen to remove excess nitrogen which could form embrittling phases in service if allowed to remain in solid solution.

Claims (14)

We claim:
1. Method for the production of titanium nitride dispersion strengthened alloys, such method including the steps of subjecting particles of titanium-containing alloy powder which also contains chromium to heating in the presence of ammonia to form a layer of chromium nitride(s) on the particles, and then to heating at a higher temperature and in an inert atmosphere to dissociate the chromium nitride(s) and to convert substantially all the titanium present to titanium nitride.
2. Method according to claim 1, wherein the titanium-containing alloy powder is a titanium-containing stainless steel powder.
3. A method according to claim 1, wherein the titanium-containing alloy powder is a titanium-containing nickel based alloy powder.
4. Method according to claim 1, wherein the powders are subsequently formed into nuclear reactor components, including fuel element containers, and having a particle size lying between 30 and 120 microns.
5. Method according to claim 4, wherein the components are tubes and are formed by powder extrusion.
6. Method according to claim 1, wherein the heating in the presence of ammonia is carried out at a temperature in the region of 700° C.
7. Method according to claim 1, wherein the subsequent heating in an inert atmosphere is homogenisation carried out at a temperature between 1000° C. and 1150° C.
8. Method according to claim 1, wherein the heating in the presence of ammonia is carried out at a temperature in the region of 700° C., and the subsequent heating in an inert atmosphere is homogenisation carried out at a temperature between 1000° C. and 1150° C.
9. Method according to claim 7, wherein the said homogenisation is achieved by heating the powder rapidly to the said temperature in an atmosphere consisting of a mixture of hydrogen and nitrogen, and extending the heat treatment beyond completion of the formation of titanium nitride together with changing the atmosphere to hydrogen whereby to remove excess nitrogen.
10. Method according to claim 8, wherein the said homogenisation is achieved by heating the powder rapidly to the said temperature in an atmosphere consisting of a mixture of hydrogen and nitrogen, and extending the heat treatment beyond completion of the formation of titanium nitride together with changing the atmosphere to hydrogen whereby to remove excess nitrogen.
11. Alloys and articles made therefrom, when produced by a method according to claim 1.
12. A method for the production of titanium nitride dispersion strengthened alloy powders, comprising the steps of subjecting particles of titanium-containing alloy powder having a particle size between about 30 and about 120 microns and which also contains chromium to heating at a temperature of about 700° C. in the presence of ammonia to form a layer of chromium nitride(s) on each individual particle, and then rapidly heating to a higher temperature between about 1000° C. and 1150° C. in an inert atmosphere to dissociate the chromium nitride(s) and to convert substantially all the titanium present to titanium nitride.
13. In a method of making nuclear reactor components comprising forming the components by powder metallurgy techniques from titanium-containing alloy powder, the improvement comprising providing titanium nitride dispersion strengthened alloy as the alloy powder by subjecting particles of titanium-containing alloy powder which also contains chromium to heating at a temperature of about 700° C. in the presence of ammonia to form a layer of chromium nitride(s) on each individual particle, and then rapidly heating to a higher temperature between about 1000° C. and 1150° C. in an inert temperature to dissociate the chromium nitride(s) and to convert substantially all the titanium present to titanium nitride, the initial alloy powder having a particle size such that the resulting titanium nitride dispersion strengthened alloy powder is of a particle size between about 30 and about 120 microns.
14. A method as claimed in claim 13 wherein the components are tubes and are formed by powder extrusion of the titanium nitride dispersion strengthened alloy powder.
US06/715,378 1984-04-06 1985-03-25 Titanium nitride dispersion strengthened alloys Expired - Lifetime US4582679A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8408901 1984-04-06
GB848408901A GB8408901D0 (en) 1984-04-06 1984-04-06 Titanium nitride dispersion strengthened alloys

Publications (1)

Publication Number Publication Date
US4582679A true US4582679A (en) 1986-04-15

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US06/715,378 Expired - Lifetime US4582679A (en) 1984-04-06 1985-03-25 Titanium nitride dispersion strengthened alloys

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US (1) US4582679A (en)
EP (1) EP0161756B1 (en)
JP (1) JPH062919B2 (en)
DE (1) DE3565409D1 (en)
GB (2) GB8408901D0 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708742A (en) * 1985-11-28 1987-11-24 United Kingdom Atomic Energy Authority Production of nitride dispersion strengthened alloys
US4846899A (en) * 1986-07-07 1989-07-11 United Kingdom Atomic Energy Authority Nitride dispersion-strengthened steels and method of making
US4999052A (en) * 1988-10-05 1991-03-12 United Kingdon Atomic Energy Authority Method of producing nitrogen-strengthened alloys
US5123972A (en) * 1990-04-30 1992-06-23 Dana Corporation Hardened insert and brake shoe for backstopping clutch
US5141574A (en) * 1988-11-10 1992-08-25 Sumitomo Metal Industries, Ltd. Process of forming dispersions in titanium alloys by melting and precipitation
US5415704A (en) * 1992-02-07 1995-05-16 Smith & Nephew Richards Inc. Surface hardened biocompatible metallic medical implants
WO1998024575A1 (en) * 1996-12-06 1998-06-11 Dynamet Technology P/m titanium composite casting
US7431777B1 (en) * 2003-05-20 2008-10-07 Exxonmobil Research And Engineering Company Composition gradient cermets and reactive heat treatment process for preparing same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE454059B (en) * 1985-09-12 1988-03-28 Santrade Ltd SET TO MANUFACTURE POWDER PARTICLES FOR FINE CORN MATERIAL ALLOYS
DE3925865C1 (en) * 1989-08-04 1991-01-10 Goetze Ag, 5093 Burscheid, De
GB9200880D0 (en) * 1992-01-16 1992-03-11 Atomic Energy Authority Uk A method of producing a surface coating upon a substrate
SE520561C2 (en) 1998-02-04 2003-07-22 Sandvik Ab Process for preparing a dispersion curing alloy
BR0010976A (en) 1999-05-27 2002-03-26 Sandvik Ab Surface modification of high temperature alloys

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4047981A (en) * 1976-06-30 1977-09-13 Armco Steel Corporation Internally nitrided ferritic stainless steel strip, sheet and fabricated products and method therefor
US4427461A (en) * 1981-11-16 1984-01-24 The Garrett Corporation Nitridation and brazing of assemblies with titanium-containing iron based alloys
US4464207A (en) * 1978-08-14 1984-08-07 The Garrett Corporation Dispersion strengthened ferritic stainless steel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2082749A5 (en) * 1970-03-25 1971-12-10 Allegheny Ludlum Steel Steel powder internally reinforced with a - dispersion of metallic nitride particles
GB2048955B (en) * 1979-04-05 1983-01-26 Atomic Energy Authority Uk Titanium nitride strengthened alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4047981A (en) * 1976-06-30 1977-09-13 Armco Steel Corporation Internally nitrided ferritic stainless steel strip, sheet and fabricated products and method therefor
US4464207A (en) * 1978-08-14 1984-08-07 The Garrett Corporation Dispersion strengthened ferritic stainless steel
US4427461A (en) * 1981-11-16 1984-01-24 The Garrett Corporation Nitridation and brazing of assemblies with titanium-containing iron based alloys

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708742A (en) * 1985-11-28 1987-11-24 United Kingdom Atomic Energy Authority Production of nitride dispersion strengthened alloys
US4846899A (en) * 1986-07-07 1989-07-11 United Kingdom Atomic Energy Authority Nitride dispersion-strengthened steels and method of making
US4999052A (en) * 1988-10-05 1991-03-12 United Kingdon Atomic Energy Authority Method of producing nitrogen-strengthened alloys
US5141574A (en) * 1988-11-10 1992-08-25 Sumitomo Metal Industries, Ltd. Process of forming dispersions in titanium alloys by melting and precipitation
US5123972A (en) * 1990-04-30 1992-06-23 Dana Corporation Hardened insert and brake shoe for backstopping clutch
US5415704A (en) * 1992-02-07 1995-05-16 Smith & Nephew Richards Inc. Surface hardened biocompatible metallic medical implants
US5498302A (en) * 1992-02-07 1996-03-12 Smith & Nephew Richards, Inc. Surface hardened biocompatible metallic medical implants
WO1998024575A1 (en) * 1996-12-06 1998-06-11 Dynamet Technology P/m titanium composite casting
US5897830A (en) * 1996-12-06 1999-04-27 Dynamet Technology P/M titanium composite casting
US7431777B1 (en) * 2003-05-20 2008-10-07 Exxonmobil Research And Engineering Company Composition gradient cermets and reactive heat treatment process for preparing same
US20080257454A1 (en) * 2003-05-20 2008-10-23 Chun Changmin Composition gradient cermets and reactive heat treatment process for preparing same

Also Published As

Publication number Publication date
JPS60230947A (en) 1985-11-16
GB8408901D0 (en) 1984-05-16
GB2156863B (en) 1987-08-19
EP0161756A1 (en) 1985-11-21
GB8506967D0 (en) 1985-04-24
GB2156863A (en) 1985-10-16
JPH062919B2 (en) 1994-01-12
DE3565409D1 (en) 1988-11-10
EP0161756B1 (en) 1988-10-05

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